Patent GB-613980-A (GB)
Title: Manufacture of new dyestuffs
Filed: 1946-07-03
Abstract: New dyestuffs are made by treating compounds of the anthraquinone series and related types as herein after defined which carry one or more chloromethyl or bromomethyl groups by known methods for replacing the chlorine or bromine atoms of the chloromethyl or bromomethyl groups by isothiouronium salt groups. The compounds of the anthraquinone series and related types referred to in this Specification are the coloured compounds which may be represented by the formula <FORM:0613980/IV (c)/1> wherein A and B may be the same or different and may be carbon, nitrogen or sulphur atoms which form part of one or more ring systems condensed with one or both of the phenylene nuclei X and Y, or may be oxygen atoms, and wherein the phenylene nuclei X and Y may carry further substituents other than sulphonic or carboxylic acid groups, or may carry rings condensed with two adjacent carbon atoms of X or Y, provided that when the number of aromatic and quinonoid rings in the condensed ring systems is less than 6 then a heterocyclic ring which forms part of the condensed ring system must carry at least one pendent aryl nucleus (free from sulphonic or carboxylic acid groups) connected directly, or X or Y or any of the condensed rings must carry at least one pendent aryl nucleus (free from sulphonic or carboxylic acid groups) connected through an -O-, -S-, -NH-, -NH-CO- or -CO-NH- linkage. Examples of starting materials which may be used in this invention include mono- and bis-(chloromethyl) - acedianthrone, bis - (chloromethyl) - dibenzanthrone, bis - (chloromethyl)-isodibenzanthrone, chloromethyl - indanthrone, the chloromethyl derivative of 8 : 17-di-p-toluidinoindanthrone, the bis-chloromethyl derivative of 2 : 8-diphenyl-11 : 21(N) : 51 : 61(N)-anthraquinonedithiazole and bis-(chloromethyl)-1 : 4-dianilino-, 1 : 4-di-p-toluidino- and 1 : 4-di - m - xylidinoanthraquinone, bis - (chloromethyl) - perylene - 3 : 4 : 9 : 10 - tetracarboxy-di-(phenylimide).  The starting materials for use in this invention may be made by reacting the compounds of the anthraquinone series and related types with dichloroor dibromodimethyl ether in the presence of a condensing agent such as for example sulphuric acid.  An example of a suitable method (1) is with such an ester as is known to convert sulphides into ternary sulphonium salts, for example with dimethyl sulphate or methyl p-toluenesulphonate.  Suitable mercaptans which may be used in this process include for example methyl-mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan, thiophenol and p-thiocresol, causing the chloro- or bromo-methyl derivatives to react with a thiourea containing at least one hydrogen atom directly attached to nitrogen so as to convert it into an isothiouronium salt.  Suitable thioureas which may be used for this purpose include thiourea, N-methyl-thiourea, N-phenyl-thiourea, N : N1-dimethylthiourea, N : N-dimethylthiourea and N : N : N1-trimethylthiourea.  In examples, tetramethylthiourea is reacted with the chlormethyl derivatives of (1) dibenzanthrone, (2) isobibenzanthrone, (3) acetianthrone, (4) indanthrone, (5) 8 : 17- di-p-toluidinoindanthrone, (6) 2 : 8-diphenyl-11 : 21 (N) : 51 : 61(N)-anthraquinonedithiazole, (7) perylene - 3 - 4 : 9 : 10 - tetracarboxy - di-(phenylimide or o-tolylimite or p-chlorphenylimide, (8) 6 - p - toluidino - 2 - phenyl - anthrapyrimidine, (9) 1 : 4 - diamino - 2 - phenoxyanthraquinone, (10) 1 : 4 - diamino - 2 : 3-di - p - tolylmercaptoanthraquinone, (11) 6-benzoylamino - 11 : 21 - phthaloyl - 51 : 61-benzcarbazole.  Also in examples, thiourea is reacted with the chlormethyl derivatives of (12) acedianthrone, (13) dibenzanthrone, (14) isodibenzanthrone, (15) perylene-3 : 4 : 9 : 10-tetracarboxy-di-(phenylimide); (16) sym.-N : N1-dimethylthiourea is reacted with perylene-3 : 4 : 9 : 10 - tetracarboxy - di - (phenylimide); (17) tetramethylthiourea is reacted with the brommethyl derivatives of acedianthrone or of 6 - p - toluidino - 3 - methyl - anthrapyridone.